Ester-linked derivatives of carbohydrates as builders for detergent compositions

ABSTRACT

1. A DETERGENT COMPOSITION COMPRISING: (A) AT LEAST ONE DETERGENT SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC, NONIONIC, ZWITTERIONIC AND AMPHOLYTIC AGENTS; (B) AN ORGANIC BIODEGRADABLE DETERGENT BUILDER COMPRISING A WATER SOLUBLE SALT OF AN ESTER-LINKED CARBOXYL DERIVATIVE OF A POLYSACCHARIDE, SELECTED FROM THE GROUP CONSISTING OF STARCH MALEATE, STARCH SUCCINATE, STARCH PHTHALATE, STARCH GLUTARATE, STARCH CITRACONATE, STARCH ITACONATE, STARCH DIGLYCOLATE AND STARCH DILACTATE WHEREIN THE D.S. VALUE RANGES FROM ABOUT 0.5-3 AND WHEREIN SAID BUILDER REPRESENTS FROM ABOUT 20% TO ABOUT 60% OF THE TOTAL WEIGHT OF THE DETERGENT COMPOSITION AND THE WEIGHT RATIO OF BUILDER TO SURFACTANT IS FROM ABOUT 1:10 TO ABOUT 50:1.

United States Patent O 3,849,341 ESTER-LINKED DERIVATIVES OF CARBOHY- DRATES AS BUILDERS FOR DETERGENT COMPOSITIONS Vincent Lamberti, Upper Saddle River, N.J., assignor to Lever Brothers Company, New York, N.Y.

No Drawing. Continuation-impart of abandoned application Ser. No. 77,052, Sept. 30, 1970. This application Feb. 1, 1972, Ser. No. 222,659

Int. Cl. C08b 19/04, 3/12; C11d 3/22 U.S. Cl. 252-546 19 Claims ABSTRACT OF THE DISCLOSURE The use of ester-linked carboxylate derivatives of carbohydrates such as sodium starch maleate, sodium cellulose phthalate, sodium glycogen-, sucroseand methyl glucoside-succinates and sodium semicellulose dilactate, as biodegradable builders in detergent compositions. The aforementioned compounds can be substituted in detergent compositions for existing builders containing phosphorus or nitrogen without impairing the efficiency of such detergent compositions.

BACKGROUND OF THE INVENTION Field of the Invention Detergent compositions containing biodegradable builders. This is a continuation-in-part of my copending application Ser. No. 77,052 filed Sept. 30, 1970 now abandoned.

DESCRIPTION OF THE PRIOR ART In recent years, studies have been conducted concerning the problem of eutrophication. Eutrophication can be defined as a natural process of enrichment of waters with nutrients, such as phosphorus and nitrogen, at a slow rate. Eutrophication can be detrimental, since it may cause increased algal growth and algal scums which are unaesthetic, odorous, distasteful and often clog filters of water treatment plants.

It has been postulated that various human activities have accelerated the process. Contributing factors in the eutrophication of lakes, streams and estuaries are natural runoff, agricultural drainage, ground water, precipitation, sewage and waste efliuents. Although there is no present adequate proof, it has been postulated that the phosphoruscontaining builders present in detergent compositions can be a factor in eutrophication, and therefore any substitutes which do not contain phosphorus may decrease to some extent the eutrophication problem. Thus, those skilled in the art have expended a great deal of time and money to find suitable material to reduce or replace the existing phosphate builders in detergent compositions. However, most builders which have been discovered to date have been unsatisfactory for one or many possible reasons and are normally less efiicient than the existing phosphorus builder materials.

The ester-linked carboxylate derivatives of alkyl glycosides, di-, oligoand poly-saccharides as builders in accordance with the present invention not only permit the reduction or replacement of existing phosphate and nitrogen-containing builders in detergent compositions without sacrificing detergency efficiency, but in addition, afford a detergent composition containing a builder which is completely biodegradable.

SUMMARY OF THE INVENTION It is an object of the present invention to provide detergent compositions containing builder compounds which are free of, or contain substantially reduced amounts of nitrogen and phosphorus, and are as efiicient as existing builders containing phosphorus and nitrogen.

It is another object of the invention to provide compositions containing builder compounds which can be synthesized from low cost raw materials at reasonable prices and are biodegradable.

Still another object of the present invention is to provide new organic compounds which may be utilized as builders in detergent compositions.

DESCRIPTION OF THE INVENTION It has now been discovered that certain ester-linked carboxylate derivatives of carbohydrates, particularly polysaccharides, such as sucrose, lactose, maltose, cellobiose, rafiinose, starches, cellulose, glycogen, hemi-celluloses, pectins, alginates and gums and carbohydrate derivatives such as alkyl glycosides can serve as effective detergent builders in detergent compositions.

The builders employed in accordance 'with the present invention can be generally described as derivatives of alkyl, glycosides, di-, oligoand poly-saccharides having the general formula FormulaI bH-O wherein A is COOM or CH OR; R is hydrogen or a carboxylate ester moiety of the formula M is an alkali metal, ammonium or substituted ammonium cation; X is phenylene, or an alkyleneoxyalkylene moiety or a straight or branched chain alkylene or alkylene group of 2-4 carbon atoms; R is R, an alkyl group containing one to four carbon atoms or an aor fl-fructose moiety having the structure wherein R is as defined above; 12 is an integer of from about 1-10,000 and wherein the average number of carboxylate ester moieties is at least 0.5 per monomeric unit. The aforementioned compounds can be substituted in detergent compositions for existing builders containing phosphorus or nitrogen without impairing the efiiciency of such detergent compositions.

The builder salts (Formula I) of the invention may be generally described as ester-linked carboxylate derivatives of carbohydrates formed by reacting an alkyl glycoside, a di-, oligoor polysaccharide with a cyclic anhydride and subsequently neutralizing the resulting acid ester with an appropriate base to form the desired esterlinked carboxylate derivative. More specifically, typical representative members of the aforementioned group of compounds include the maleate, succinate, phthalate, glutarate, adipate, citraconate, itaconate, dilactate and diglycolate ester salts of a di-, oligoor poly-saccharide such as sucrose, hydrolyzed starch, starch, cellulose, glycogen, semicellulose, alginic acid, and of an alkyl glucoside such as methyl or ethyl glucoside.

The aforementioned compounds are for the most part known compounds and their method of preparation is described in the art [Mullen and Pacsu, Ind. Eng. Chem. 35 381 (1943); ibid. 34 1209 (1942); Malm and Fordyce, ibid. 32 405 (1940)]. In general, the builders used in the invention may be prepared by heating the particular ca bohydrate with a cyclic anhydride in a suitable solvent such as toluene or pyridine and, after solvent removal, purified by washing either with water or dilute mineral acid. (The D.S. value is controlled by the ratio of the anhydride to starting carbohydrate used.) An aqueous solution or slurry of the acid ester is then neutralized to a pH of -8-8.'6 with the desired base: e.g. sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, lithium carbonate, ammonium hydroxide, tetramethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine and morpholine to form the corresponding alkali metal, ammonium or substituted ammonium salts. In the cases where the acid ester is water soluble, the acid ester may be purified by first dissolving in water and neutralizing to pH 8.0 with an alkali metal bicarbonate or carbonate, evaporating to dryness and then extracting with a lower alcohol (e.g. methanol or ethanol) to separate the desired product. Accordingly, by heating an alkyl glycoside, a di-, oligoor poly-saccharide with succinic, glutaric, maleic, phthalic, citraconic, itaconic, dilactic or diglycolic anhydrides, there is formed the corresponding succinate, glutarate, maleate, phthalate, citraconate, itaconate, dilactate, or diglycolate acid ester of the alkyl glycoside, di-, oligoor poly-saccharide which are subsequently neutralized with the appropriate base to form the builder salts of the invention. For convenience the invention will hereinafter, except where noted, be described with reference to polysaccharides.

Furthermore, it should be understood that the above structure (Formula I), for purposes of simplicity, is entirely pictorial and represents a simplified version of the molecule. More specifically, it is well known, for example, that many starches can contain as a major constituent thereof, amylopectin or the branched chain as opposed to the amylose or linear chain molecule which is actually indicated by the pictorial representation above. Since the amylopectin polymers are linked by hemiacetal links at the uronic position, the ester-linked carboxylate derivatives of starches described in the present invention may also contain considerable branching at the uronic positions with hemiacetal-linked polyglucoside chains.

In the case of cellulose, the anhydroglucose unit depicted bove (Formula I) is linked as in cellobiose and may contain from about 250-2500 cellobiose units per molecule. Accordingly, it should be understood that when the degree of substitution or D.S. value (i.e., number of R groups per monomeric unit) is stated, it is the average number of R groups per anhydroglucose unit that is intended in the cases of cellulose and starch.

Further, in the case where alginic acid (A=COOH) is used as a starting material to prepare derivatives of the invention, the repeating unit is even more complex and consists of a 8(1-4) linked anhydro-D-mannuronic acid and anhydro-L-gluuronic acid moiety. Again, when referring to the degree of substitution, the average number of R groups per anhydromonosaccharide unit is intended.

It is further apparent that, with the exception of the cases where all available hydroxyl groups are substituted by an ester carboxylate moiety, there is a complex distribution of R substitutents in the polymer molecule. Thus, some anhydromonosaccharide units may be monosubstituted, some may be disubstituted, some may be trisubstituted and some may be unsubstituted. Further, the sequence of such substituted and unsubstituted units, while unknown, is most probably in a random manner.

- As a result of the complex structures present in the polysaccharide ester salts in the present invention, the degree of substitution or esterification is deferred to by the average number of ester carboxylate moieties attached per anhydromonosaccharide unit. A degree of substitution of 0.5, for example, indicates that, on the average, for every 100 anhydromonosaccharide units in the molecule, there are 50 ester carboxylate moieties in the complex arrangement described above.

In the cases of the builder salts derived from the alkyl glycosides with n=1 and the disaccharides, the D.S. value refers to the total number of hydroxyl groups substituted by ester carboxylate moieties per molecule. Thus, the D.S. value may be as high as 4 in the alkyl glycoside derivatives and as high as 8 in the disaccharide derivatives.

The degree of substitution or esterification can be readily determined by those skilled in the art, such as by titrating the acid ester with standard alkali. 7

It has been found that effective detergent-building properties are afforded when the polysaccharide ester salts of the present invention have a degree of substitution (D.S. value) of from about 0.5-3, preferably about 1-3 and more preferably, 1.5-3. In the cases of the ester salts of the disaccharides, effective detergent-building properties are afforded when the D.S. value is from about 1 to 8 and preferably from about 2 to 8. In the cases of the ester salts of the alkyl glycosides, the effective detergent building properties are afforded when the D.S. value is from about 1 to 4 and preferably, from about 2 to 4.

Any carbohydrate, especially polysaccharides, containing hydroxy groups may be used as a starting material for forming the derivatives used in the present invention including such substances as the (C to C alkyl glycosides, exemplified by methyl and ethyl glucopyranosides; disaccharides, exemplified by sucrose, lactose, maltose and cellobiose; trisaccharides such as rafiinose; oligosaccharides, exemplified by those obtainable by enzymatic hydrolysis of corn starch and cellulose, polysaccharides, exemplified by glycogen, starches such as those derived from corn, potato, rice, arrowroot, tapioca, wheat, sago, etc., cellulose, hemicelluloses, polyuronic acids, dextrans, pectins, alginic acid and natural gums such as arabic and acacia as well as any of the aforementioned carbohydrates that may be modified by etherification, carboxymethylation or cross-linking. The preferred builder salts used in the composition of the present invention are the salts of the succinate and maleate ester derivatives of starch, hydrolyzed starch, cellulose and sucrose.

The preferred cations for use in the compositions of the present invention are alkali metal, alkanolammonium (i.e., mono-, diand tri-ethanolammonium), ammonium and mixtures thereof. Those especially preferred are sodium, potassium and triethanolammonium, although any cation which will solubilize the carbohydrate ester salt is suitable for use in the present invention.

According to the present invention, excellent cleaning results can be obtained by using the builder salts described above with a wide range of detergent surface active materials and mixtures thereof. The builder salts can be used singularly, in combination with each other as the sole builder in the detergent composition or in combination with other builders such as sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, sodium tripolyphosphate, sodium and potassium pyrophosphate, sodium carbonate, sodium polyacrylate, oxidized starches, trisodium citrate and trisodium carboxymethyloxysuccinate.

In the detergent compositions of the present invention, the only essential ingredients are the detergent surface ac tive material and the builder salt. The weight percent of the builder present in the detergent composition will range from about 5 to about and preferably from about 20 to about 60% and more preferably 35-50% by weight of the total weight of the composition. When expressed as a weight ratio of builder to surfactant, the builders used in the instant invention will generally 'be present in a ratio of about 1:10 to about 10:1, and preferably 2:1- 5:1 depending on the end use or whether a heavy-duty or light-duty detergent is desired.

Similarly, in detergent compositions suitable for washing dishes in mechanical dishwashers, the ratio of builder to detergent may be as high as 50:1.

In addition to having detergent building properties, the ester carboxylate derivatives of the polysaccharides described in the present invention may also be used as antiredeposition agents in detergent compositions. When used for such purposes, the ester carboxylate polysaccharide derivative is generally present in minor amounts in relation to the total weight of the composition. For example, as a rule, when employed as an antiredeposition agent, the polysaccharide derivatives of the invention will gen erally comprise up to 5% (preferably 13%) of the total Weight of the detergent composition.

The detergent surface active compounds which can beused in the compositions of this invention include anionic, nonionic, zwitterionic, ampholytic detergent compounds and mixtures thereof. These suitable substances are outlined-at length below.

(a) Anionic detergent compositions which can be used in the compositions of this invention include both soap and non soap detergent compounds. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium or potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap and tall oil soap. Examples of anionic organic non-soap detergent compounds are the water soluble salts, alkali metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the synthetic detergents which form a part of the compositions of the present invention are the sodium or potassiumalkyl sulfates especially those obtained by sulfating the higher alcohols (Cy-C1 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzenesulfonates in which the alkyl group contains from about 9 to about 20 carbon atoms and in which the benzene ring is attached to the alkyl chain at either the one position or at the secondary positions such as in sodium linear secondary (C -C alkyl benzenesulfonate, sodium p-(2-dodecyl)benzenesulfonate, sodium p-(2-octadecyl)benzenesulfonate, sodium p-(3-dodecyl)benzenesulfonate and 3-phenyldodecanesulfonate; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid estersof the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about lto'6 moles of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 18 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl taurine in which the fatty acids, for example, are derived from tallow; alkane sulfonates such as those derived by reacting alpha-olefins containing 8 to 20 carbon atoms with sodium bisulfite and those derived by reacting paraffins with S0 and C1 and then hydrolyzing with a base to produce a random sulfonate; alphaolefin sulfonates such as those derived by reacting alphaolefins with S0 and then neutralizing the reaction product; and others known in the art.

-(b) Nonionic synthetic detergents may be broadly defined as compounds which do not ionize in water solution. For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name of -Pluronic. These compounds are formed by condensing ethylene oxide with an hydrophobic base formedby the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1,500 to 1,800. The addition of polyoxyethylene radcals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point Where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkylphenols, e.g., the condensation products of alkylphenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkylphenols. The alkyl substituent in such compounds may be derived from polymerized propylene, di-isobutylene, octene, dodecene or nonene, for example.

(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said hydrophobic base having a molecular weight of the order to 2,500 to 3,000, are satisfactory.

(3) The condensation product of primary or secondary aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 3 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms; a random linear secondary alcohol containing ll-15 carbon atoms derived from n-paratfins and condensed with 3-20 moles of ethylene oxide per mole of the alcohol.

(4) Long chain tertiary amine oxides corresponding to the following general formula, R R R N 0, wherein R is an alkyl radical of from about 8 to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethyl radicals. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide and dimethylhexadecylamine oxide, N-bis(hydroxyethyl)dodecylamine oxide.

(5) Long chain'tertiary phosphine oxides corresponding to the following formula RRRP- O, wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:

dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide,

bis (hydroxymethyl dodecylphosphine oxide, bis Z-hydroxyethyl) dodecylphosphine oxide, Z-hydroxypropylmethyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-Z-hydroxydodecylphosphine oxide.

(6) Dialkyl sulfoxides corresponding to the following formula, RR'S 0, wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical or an alkyl or betaor gamma-monohydroxyalkyl radical containing one or two other oxygen atoms in the chain, the R groups ranging from to 18 carbon atoms in chain length, and wherein R is methyl, ethyl or alkylol. Examples of suitable sulfoxide compounds are:

dodecyl methyl sulfoxide,

tetradecyl methyl sulfoxide,

3-hydroxytridecyl methyl sulfoxide, 2-hydroxydodecyl methyl sulfoxide, 3-hydroxy-4-decyloxybutyl methyl sulfoxide, 3-hydroxy-4-dodecyloxybutyl methyl sulfoxide, 2-hydroxy-3-decyloxypropyl methyl sulfoxide, 2-hydroxy-3-dodecyloxypropyl methyl sulfoxide, dodecyl ethyl sulfoxide,

2-hydroxydodecyl ethyl sulfoxide, and dodecyl-Z-hydroxy ethyl sulfoxide.

(c) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are sodium-3- dodecylaminopropionate and sodium-3-dodecylaminopropane-sulfonate and sodium N-Z-hydroxydodecyl-N-methyl-taurate.

(d) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, sulfonium compounds and phosphonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are 3-- (N,N-dimethyl-N-hexadecylammonio)propane l sulfonate. Examples of compounds falling within this definition are 3- N,N-dimethyl-N-hexadecylammonio propane- 1 sulfonate, 3-(N,N-dimethyl-N-hexadecylarnmonio)-2 hydroxypropane-l-sulfonate, 3-(dodecylmethylsulfonium) propane sulfonate, and 3-(cetylmethylphosphonium)ethane sulfonate.

In addition to the essential ingredients in the detergent composition, other optional ingredients may also be added. Examples of the optional ingredients are perfumes, colorants, fabric softening agents, fungicides, germicides, enzymes, fluorescent dyes, antiredeposition agents, hydrotropes and in the case of liquid compositions, opacifiers and organic solvents. Other ingredients such as bleaches, i.e., sodium perborate with or without activators, active chlorine compounds, and inorganic salts such as sodium carbonate, sodium bicarbonate, sodium sulfate, sodium chloride and sodium silicate may also be present.

The detergent compositions of the present invention can be utilized in washing solutions over a pH range of from about 7-11 and more preferably 8-10.

Tables I-VIII further illustrate the present invention. The detergent formulations set forth in the Tables represent detergent compositions containing representative classes of surface active ingredients in combination with builders of the present invention and also standard phosphate and nitrogen-containing builders. The compositions were prepared by blending together the recited components in the proportions indicated, including an anticorrosion agent and buffering agent (sodium silicate) and adjusting the pH where necessary by the addition of sodium hydroxide. The compositions were then tested for detergency or cleaning ability in the Terg-O-Torneter test wherein washing conditions are as indicated and the results reported as detergency units. The average detergency units (DU) of the formulation is the final reflectance value of the washed cloth minus the initial reflectance of the soiled cloth (the average of two runs), the reflectance values being obtained by measurement with a Gardner automatic color difference meter, Model AC-3.

TABLE I.-COMPARISON OF DETERGENCY BUILDING- PROPERTIES OF SODIUM CORN STARCH SUCCINATE INORGANIC PHOSPHATE IN DETERGENT SYS- [Washing conditions: TcrgO-Tometer detergency; Dacron/Cotton Soil Cloth (vacuum cleaner dust); 120 F; 180 p.p.m. hardness (2:1 Ca Mg); 0.2% formulation concentration; pH=10.0]

Formulation (percent) Component 1 2 3 4 5 6 7 8 Anionic surfactant 18 Nonionic surfactant h Ampholytic surfactant C Sodium corn starch succinate (D.S.=1.9)

Sodium trrpolyphos Detergency urn Percent efficiency (formulation 1 vs. 2, gvs. 4, 5 vs. 6, 7 vs.

e Sodium linear alkyl (Cw-C15) secondary benzene sulfonate.

Adduct of a modified OXO-type Ctr-C15 alcohol with an average of 11 moles of ethylene oxide (i.c., N eodol 45-11 available from Shell Chemical Company).

0 Sodium N-2-hydroxy C -C15 alkyl-N-methyltaurate.

d Balance to TABLE II.COMPARISON OF DETERGENCY BUILDING PROPERTIES OF SODIUM TAPIOCA STARCH SUCCINATE WITH INORGANIC PHOSPHATE [Washing conditions: Terg-O-Tometer detcrgency; Dacron/Cotton Soil Cloth (vacuum cleaner dust); F; p.p.m. hardness (2:1 Ca**/ Mg); 0.2% formulation concentration; pH=10.0]

Sodium linear secondary (Cm-C15) alkyl benzenesulfonate. Balance to 100%.

TABLE III.COMPARISON OF DETERGENCY BUILDING PROPERTIES OF SODIUM CORN STARCH MALEA'IE WITH INORGANIC PHOSPHATE BUILDER [Washing conditions: Terg-O-Tometer detergency; Dacron/Cotton Soil Cloth (vacuum cleaner dust); 120 F; 180 ppm. hardness (2:1 Ca++/ l\lg++); 0.2% formulation concentration; pH=10.0}

Formulation (percent) Component 1 2 Anionic surfactant 18 18 Sodium corn starch maleate (D.S.=1) 50 Sodium tripolyph 50 Sodium silicate (S102: NazO =24: 1) 10 10 Water Detergency units 21. 2 25. 4

Percent eificicncy (formul e Sodium linear secondary (Cm-C15) alkyl benzenesulfonate. b Balance to 100%.

TABLE 1V.COMPARISON OF DETERGENCY BUILDING PROPERTIES OF SODIUM STARCH PHTHALATE WITH INORGANIC PHOSPHATE BUILDER Washing conditions: 'Ierg-O-Tometer detergency; Dacron/Cotton Soil Cloth (vacuum cleaner dust); 120 F; 180 p.p.rn.hardness (2:1 Ca**/ Mg); 0.2% formulation concentration; pH =10.0]

Formulation (percent) Component 1 2 Anionic surfactant e 18 18 Sodium corn starch phthalate (D.S.=3) 50 Sodium tripolyphns ham 50 Sodium silicate (SiOziNflzO =2.4:1) 10 10 Water Detergency 23. 5 29. 5

Percent efficiency (formulation 1 vs. 2)

e Sodium linear secondary (Cw-C15) alkyl benzenesulfonate. Balance to 100%.

TABLE V.COMPARISON OF DETERGENCY BUILDING PROPERTIES OF SODIUMPCELLULOSE SUOCINA'IE WITH INORGANIC HOSPHATE IN DETERGENT SYSTEMS [Washing conditions: Same p.p.m. water (2:1 Ca++/ll Ig*+)] as Table I except for formulation 1 and 2 which were run in 90 Formulation (percent) Nonionic surfactant n. Ampholytic surfactant v Zwitterionic surfactant d Anionic surfactant 18 18 Sodium cellulose succinate (D. 50 50 50 50 Sodium tripolyphosphate- 50 50 50 50 50 Sodium silicate (Si0z:Naz

U) (0 (0 (0 (0 U) (0 A V 24.6'26.2 24.6 25.7 22.5 26.5 Percent efiiciency (to tion 1 vs. 2, 3 vsni, 5 vs- 6 .7 vs. 8,9vs.10) 96 94 94 96 85 B Sodium linearsecondary (Cm-C15) alkyl benzenesulionate.

Addnct of a modified OXO-type CIA-C15 alcohol with an average of 11 moles of ethylene oxide (i.e., Neodol 45-11 available from Shell.)

6 Sodium N-2'hydroxy Cir-Cu alkyl-N metl1yltaurate. Cocodimethylsulfo ropyl betaine. Q Alkene sulfonates Ola-C15). Balance to 100%. 7

[Washing conditions: 'Ierg-O-Tometer detergency; Dacron/Cotton Soil Cloth (vacuum cleaner dust); 120 F; 180 ppm. hardness (2:1 Cafi' Mg++); 0.2% formulation concentration; .pH=10.0]

' Formulation (percent) Component- Anionic surfactant I Sodlum'eellulose suecinate (D.S

1. Sodium tripolyphosphate. Sodium silicate (SiOzzNazO- 10 10 10 10 v 10 Water Detergency units 9. 3 12. 6 29. 1 29. 5 25. 2 25.1 Percent efficiency (formulation 1 vs.

2, 3 vs. 4, 5 vs. 6) 74 99 100 e Sodium linear secondary (Clo-015) alkyl benzenesulionate. b Balance to 100%.

TABLE VIL-DETERGENCY BUILDING PROPERTIES OF SODIUM OELLULOSE SUCCINATE IN COMBINATION WITH INORGANIC BUILDERS [Washing conditions: Terg-O-Tometer detergency; Dacron/Cotton Soil Cloth (vacuum cleaner dust); 120 F;- 180 p.p.m. hardness (2:1 Ca Mg); 0.2% formulation concentration; pH=10.0]

' Formulation (percent) Component 1 2 3 V p '4 Anionic surfactant 18 18 18 18 Sodium cellulose succinate (D. 25 25 Sodium tripolyphosphatenu 25 50 Nitrilotriacetate (Nils) 25 50 Sodium silicate (SiOnNarO =2 1) 10 10 10 10 Water; Detergency units 23. 5 23. 9 28. 9 29. 9 Percent etficiency (formulation 1 vs. 2, 97

H Sodium linear secondary (Cm-C) alkyl benzenesulfonate. Balance to 100%.

TABLE VIII.-COMPARISON OE DETERGENGY BUILDING PROPERTIES OF SODIUM SUOROSE SUCCINATES WITH INORGANIC PHOSPHATE IN A DETERGENT SYSTEM [Washing conditions: Terg-O-Tometer detergency; Dacron/Cotton Soil Cloth (vacuum cleaner dust); 120 F; 180 ppm. hardness (2:1 Ca++l Ma 0.2% formulation concentration; pH=10.0]

r Detergeney(DU s)-. 28.8 23.5 25.0 31.4 13.2 12.2 26.7 Percent eiliciency relative to control formulation 75 80 40 46 l Sodium linear secondary (Cm-C15) alkyl benzenesullonate. Balance.

From the above Tables, it is clear that the ester-linked carboxylate derivatives of carbohydrates used in the present invention may be eifectively used as builders in detergent compositions containing all classes of synthetic surface active agents, either as the sole detergent building agent or in combination with phosphorus-containing or nitrogen-containing detergent builders.

EXAMPLE I Preparation of Sucrose Succinate Sucrose 25 g. (0.073 mole) is added to 200 ml. of pyridine and after heating to C., 60 g., (0.60 mole) of succinic anhydride is added. The resulting solution is then concentrated to remove solvent and the residue obtained dissolved in water to which is gradually added 64 g. (0.60 mole) of sodium carbonate. The mixture is then freeze-dried and the product obtained extracted with anhydrous methylalcohol at room temperature, filtered, concentrated and, then precipitated from solution with acetone to aflordy53.63 g. havinga D.S. value of 4.3.;

By increasing or lowering the ratio of succinic anhydride to sucrose the'D.S. value can be correspondingly increased or decreased.

Having described and set forth the best mode for carrying out the invention, modifications within the spirit thereof will occur to persons skilled in the art, it will be understood that the invention is not restricted to the exemplified embodiments, but is limited only by the scope of the appended claims.

What is claimed is:

1. A detergent composition comprising:

(a) at least one detergent surface active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic agents;

(b) an organic biodegradable detergent builder comprising a water soluble salt of an ester-linked carboxyl derivative of a polysaccharide, selected from the group consisting of starch maleate, starch succinate, starch phthalate, starch glutarate, starch citraconate, starch itaconate, starch diglycolate and starch dilactate wherein the D.S. value ranges from about 0.5-3 and wherein said builder represents from about 20% to about 60% of the total weight of the detergent composition and the weight ratio of builder to surfactant is from about 1:10 to about 50:1.

2. A detergent composition comprising:

(a) at least one detergent surface active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic agents;

(b) an organic biodegradable detergent builder comprising a water soluble salt of an ester-linked carboxyl derivative of oligosaccharide selected from.

the group consisting of hydrolyzed starch maleate, hydrolyzed starch succinate, hydrolyzed starch phthalate, hydrolyzed starch glutarate, hydrolyzed starch citraconate, hydrolyzed starch itaconate, hydrolyzed starch diglycolate and hydrolyzed starch dilactate wherein the D8. value is from about 1-3 and wherein said builder represents from about 20% to about 60% of the total weight of the detergent composition and the weight ratio of builder to surfactant is from about 1:10 to about 50:1.

3. A composition of Claim 1 wherein the detergent surface active agent is anionic.

4. A composition of Claim 1 wherein the detergent surface active agent is nonionic.

5. A composition of Claim 2 wherein the detergent is an anionic surface active agent.

6. A composition of Claim 2 wherein the detergent is a nonionic surface active agent.

7. A composition of Claim 1 wherein the biodegradable detergent builder is an ester salt of a starch derived from corn, potato, rice, arrowroot, tapioca, wheat or sago.

8. A composition of Claim 2 wherein the biodegradable detergent builder is an ester salt of a hydrolyzed starch derived from corn, potato, rice, arrowroot, tapioca, wheat or sago.

9. A composition of Claim 1 wherein the biodegradable detergent builder is a salt of sodium, potassium, lithium, ammonia, monoethanolamine, diethanolamine, triethanolamine or morpholine.

10. A composition of Claim 2 wherein the biodegradable detergent builder is a salt of sodium, potassium, lithium, ammonia, monoethanolamine, diethanolamine, triethanolamine or morpholine.

11. A composition of Claim 1 wherein the biodegradable detergent builder is a starch succinate.

12. A composition of Claim 1 wherein the biodegradable detergent builder is sodium corn starch succinate.

13. A composition of Claim 1 wherein the biodegradable detergent builder is a starch maleate.

14. A composition of Claim 1 wherein the biodegradable detergent builder is a starch phthalate.

15. A composition of Claim 1 wherein the weight ratio of builder to surfactant is from about 1:10 to about :1.

16. A composition of Claim 1 wherein the weight ratio of builder to surfactant is from 2:1 to 5:1.

17. The composition of Claim 2 wherein the weight ratio of builder to surfactant is from about 1:10 to about 18. A composition of Claim 2 wherein the wegiht ratio of builder to surfactant is from 2:1 to 5:1.

19. A composition of Claim 1 wherein the biodegradable detergent constitutes 35 to by weight of the total weight of the composition.

References Cited UNITED STATES PATENTS 2,505,561 4/1950 McIntire 260-224 2,311,008 2/1943 Tucker 210-23 2,264,103 11/1941 Tucker 210-23 2,233,475 3/1941 Dreyfus 260-214 X 2,148,951 2/1939 Maxwell 260-209 2,108,455 2/1938 Stone 260-224 X 2,093,462 9/1937 Malm 260-224 3,723,322 3/1973 Diehl 252-89 3,629,121 12/1971 Eldib 252-89 3,308,067 3/1967 Diehl 252-559 2,891,947 6/ 1959 Paschall 260-233.5 2,868,780 1/1959 Minkema. 260-233.5 2,853,484 9/1958 Lolkema 260233.3 2,825,727 3/1958 Caldwell 260-233.3 2,759,787 8/1956 Touey 260-224 X 2,661,349 12/1953 Caldwell 260-224 2,622,997 12/ 1952 Lolkca 260-224 2,613,206 10/1952 Caldwell 260-2335 FOREIGN PATENTS 699,530 11/1953 Great Britain 260-233.5

US. or. x.-R.

252-89, 132, 135, 180, Digests 2, 11 & 15; 260-209.5, 209.6, 210 R, 224, 233.5, 234R 

1. A DETERGENT COMPOSITION COMPRISING: (A) AT LEAST ONE DETERGENT SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC, NONIONIC, ZWITTERIONIC AND AMPHOLYTIC AGENTS; (B) AN ORGANIC BIODEGRADABLE DETERGENT BUILDER COMPRISING A WATER SOLUBLE SALT OF AN ESTER-LINKED CARBOXYL DERIVATIVE OF A POLYSACCHARIDE, SELECTED FROM THE GROUP CONSISTING OF STARCH MALEATE, STARCH SUCCINATE, STARCH PHTHALATE, STARCH GLUTARATE, STARCH CITRACONATE, STARCH ITACONATE, STARCH DIGLYCOLATE AND STARCH DILACTATE WHEREIN THE D.S. VALUE RANGES FROM ABOUT 0.5-3 AND WHEREIN SAID BUILDER REPRESENTS FROM ABOUT 20% TO ABOUT 60% OF THE TOTAL WEIGHT OF THE DETERGENT COMPOSITION AND THE WEIGHT RATIO OF BUILDER TO SURFACTANT IS FROM ABOUT 1:10 TO ABOUT 50:1. 